全高分子太阳能电池活性层相分离结构调控
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摘要
全共轭聚合物太阳能电池具有给受体能级可调、吸收范围宽及可溶液加工等优势,已经成为太阳能电池领域发展趋势.在开发高性能材料及器件结构优化的推动下,能量转换效率已经突破9%.然而,共轭聚合物分子刚性及分子结构各向异性等特点,导致全共轭聚合物共混体系相分离及结晶行为复杂,相区尺寸及界面处分子取向可控性差,难于深入理解并认识活性层结构对器件光物理过程的影响.本文从热力学及动力学角度入手,详述了全共轭聚合物共混体系相分离结构、相区尺寸及界面分子取向的可控调节.共混体系中分子迁移能力及溶液相分离类型是影响相分离结构的本质因素,并通过改变给受体比例及分子规整度等实现了孤岛、双连续及互穿网络结构的构筑.同时,通过添加第3组分调节溶剂-溶质分子间相互作用或聚合物分子间相互作用,在不降低活性层结晶性的基础上实现了相区尺寸的调控.最后,利用附生受限结晶原理及溶液状态,通过改变分子运动能力及在溶液中聚集程度,实现了由edge-on到face-on取向的转变.
Compared to the polymer/fullerene system,all-polymer solar cells,based on conjugated polymers as both donor and acceptor,have many potential advantages such as achieving more efficient light absorption and high open-circuit voltage,as well as easily solution processing and large-area fabrication.Strongly promoted by developments of materials and device structure,the power conversion efficiency(PCE) has been reached 9%.However,conjugated polymers have more rigid molecules compared to the flexible polymers and thus will form chain entanglement and π-π interaction with each other,leading to a more complex phase separation process in the conjugated polymer system.Besides,the strong molecular interaction between donor and acceptor polymers may generate a long-range phase domain in the blend films,which will inhibit the excitons to diffuse to the donor/acceptor(D/A) phase interface.In addition,the difference of thermodynamics steady state between the donor and the acceptor polymers may lead to the formation of different molecular orientation,which will impede the exciton dissociation.To solve these problems,by tuning the thermodynamic and dynamics factors,including molecular rigidity and blend ratio,the phase-separated structure of the conjugated polymer blend system was adjusted and the phase separation mechanism was identified,based on which the phase diagram of the conjugated polymer blend was depicted.By controlling phase separation structure,the interpenetrating networks were obtained,facilitating the charge transfer and collection.Besides,the domain size and film crystallinity were adjusted by reducing the solvent-polymer interaction parameter and polymer-polymer interaction parameters.Due to the decreased domain size,the efficiency of the exciton diffusion was enhanced.In addition,the solution state or molecular diffusion rate was adjusted to adjust the molecular orientation.By increasing the aggregation of the polymers in solution and introducing the epitaxial crystallization,the molecular orientation could change from edge-on to face-on.The identical molecular orientation for the donor and the acceptor improved the exciton dissociation efficiency and the device performance.
Compared to the polymer/fullerene system,all-polymer solar cells,based on conjugated polymers as both donor and acceptor,have many potential advantages such as achieving more efficient light absorption and high open-circuit voltage,as well as easily solution processing and large-area fabrication.Strongly promoted by developments of materials and device structure,the power conversion efficiency(PCE) has been reached 9%.However,conjugated polymers have more rigid molecules compared to the flexible polymers and thus will form chain entanglement and π-π interaction with each other,leading to a more complex phase separation process in the conjugated polymer system.Besides,the strong molecular interaction between donor and acceptor polymers may generate a long-range phase domain in the blend films,which will inhibit the excitons to diffuse to the donor/acceptor(D/A) phase interface.In addition,the difference of thermodynamics steady state between the donor and the acceptor polymers may lead to the formation of different molecular orientation,which will impede the exciton dissociation.To solve these problems,by tuning the thermodynamic and dynamics factors,including molecular rigidity and blend ratio,the phase-separated structure of the conjugated polymer blend system was adjusted and the phase separation mechanism was identified,based on which the phase diagram of the conjugated polymer blend was depicted.By controlling phase separation structure,the interpenetrating networks were obtained,facilitating the charge transfer and collection.Besides,the domain size and film crystallinity were adjusted by reducing the solvent-polymer interaction parameter and polymer-polymer interaction parameters.Due to the decreased domain size,the efficiency of the exciton diffusion was enhanced.In addition,the solution state or molecular diffusion rate was adjusted to adjust the molecular orientation.By increasing the aggregation of the polymers in solution and introducing the epitaxial crystallization,the molecular orientation could change from edge-on to face-on.The identical molecular orientation for the donor and the acceptor improved the exciton dissociation efficiency and the device performance.
引文
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